CN102909024A - Two-step three-effect non-noble metal catalyst for purification of automobile exhaust - Google Patents
Two-step three-effect non-noble metal catalyst for purification of automobile exhaust Download PDFInfo
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Abstract
The invention relates to two-step three-effect non-noble metal catalyst for purification of automobile exhaust. A two-step carrier includes a ceramic carrier and a metal carrier. The metal carrier is made from stainless steel or nickel-chromium-aluminum alloy and needs surface pretreatment, and the specific area of the metal carrier pretreated is 100m<2>/g. Primary catalyst is rare earth-transition metal oxide in the structure of Ln1-xMxBO3 (Ln refers to a rare-earth element, M refers to an alkaline earth metal element, B refers to a transition metal element, and x=0-1). The catalyst is nano-catalyst especially responsible of oxidizing hydrocarbons, carbon monoxide and carbon granules, and is capable of fully oxidizing the carbon monoxide into carbon dioxide at 100 DEG C, oxidizing hydrocarbons into carbon dioxide and water at more than 500 DEG C, and oxidizing the carbon granules into carbon dioxide at more than 400 DEG C. Secondary catalyst made from nano fiber of Ln2-xBxCuO4 (Ln refers to a rare earth element, B refers to Ce and Sr, and x=0-1) has specific area of 105m<2>/g. The nano fiber catalyst Ln2-xBxCuO4 is capable of fully disintegrating NO into nitrogen and oxygen at 300 DEG C. The catalysts co-act so that hydrocarbons, carbon monoxide granules and nitric oxides in the exhaust can be fully converted into harmless substances, namely carbon dioxide, water, nitrogen and oxygen.
Description
Technical field
The present invention relates to a kind of for Vehicle Exhaust Gas Cleaning Catalysts such as gasoline car, diesel vehicle, motorcycle and preparation method thereof.Catalyst is two kinds of catalyst coupling work, does not contain precious metal, and nitrogen oxide, hydrocarbon, carbon monoxide and the carbon granule in the tail gas is converted into innocuous gas nitrogen, oxygen, carbon dioxide and water the most at last.Catalyst is nano transition metal-complex rare-earth oxidate containing valuable metal, and catalyst carrier is ceramic honey comb and wire netting.
Background technology
Vehicle exhaust is very serious to the pollution of environment and city dweller's health hazard; administer or the control motor vehicle exhaust emission; the key subjects that whole world field of environment protection needs to be resolved hurrily have been become; the main component of vehicle exhaust is carbon monoxide (CO); hydrocarbon (HnCm); nitrogen oxide (NOx); carbon granule PM2.5 and a small amount of plumbous compound and sulfide etc.; in general; realize that purifying vehicle exhaust has two kinds of methods: engine interior control and external engine purify; control is exactly to utilize the course of work of engine own to reduce automotive emissions in the machine; countries in the world automobile production producer has taked respectively a lot of measures at carburetor and context engine; such as electronic fuel injection; lambda sensor control technology etc.; all these measures have certain effect to reducing automotive emissions; but act on limited; even have also can serve adverse influence to dynamic property and the economy band of engine; and by comparison; the external engine that exhaust purifier is housed purifies unique advantage, becomes current solution automotive emissions the most effective most important means.It is to install cleaning catalyst additional at the exhaust pipe position that external engine purifies, with carbon monoxide (CO), hydrocarbon (H
nC
m), nitrogen oxide (NO
x) three kinds mainly contain pest and be converted into simultaneously harmless object carbon dioxide, water, nitrogen, oxygen.This kind catalyst is called as three-way catalyst or three-way catalyst.
Catalyst is the core of purifying vehicle exhaust.The basic demand of automobile exhaust purifier catalyst system therefor sums up: (1) must adapt to the acute variation of frequent, a large amount of gas shocks and temperature and component; (2) must have simultaneously high temperature (more than 800 ℃) and low temperature active, the performance catalytic action is not sintered under the high temperature during guarantee cold start; (3) can purify simultaneously CO, HC and NO
xThree kinds of harmful substances.Can satisfy simultaneously the catalyst of these conditions seldom, so tai-gas clean-up catalyst is one of problem of difficulty maximum in the heterogeneous catalysis field.Owing to technical know-how, the development of catalyst is upgraded slower in addition.The catalyst activity component is comprised of precious metals such as platinum (Pt), rhodium (Rh), palladiums (Pd) basically at present.Such catalyst cost is too high, sometimes even be equivalent to 1/10th of a vehicle price; Especially Pt, Rh more are subject to the restriction of resource.To purifying NO
xWhat play a major role is rhodium, the rhodium that is used at present cleaning catalyst for tail gases of automobiles accounts for 80% of Gross World Product, estimate that supply will present tense situation from now on, in order to alleviate the particularly contradiction between the supply and demand of Rh of Pt, now be widely used the relatively cheap but still very expensive palladium of price, developed catalyst and full palladium catalyst that Pt, Rh and Pd form.But the resource of palladium is very limited, also very expensive and easy high temperature loss of price also.Rare earth element is the most effective tai-gas clean-up catalyst and additive except precious metal.China also is the world main rare earth state of origin, and country is defined as strategic resource to rare earth, the outlet of limiting the quantity of, and the utilization of exploitation rare earth is China scientist's task and advantage.
Cleaning catalyst for tail gases of automobiles need to load on the porous carrier of high surface area, to strengthen the decentralization of catalyst, reduce the consumption of catalyst, increase the transmitance of gas, improve the mechanical strength of catalyst, generally all use honeycomb ceramic carrier, honeycomb ceramic carrier has similar favose structure, it has low bulk, high strength, resistance to heat shocks is good, adsorptivity is strong, the advantage such as wear-resistant, the multiplex cordierite of honeycomb ceramic carrier (Almasilate) is made raw material at present, cordierite not only has the low coefficient of expansion, good resistance to chemical corrosion and good heat resistance (1400 ℃ of safe handling temperature), and the porosity of itself is higher, water absorption rate can reach about 30%, be comparatively ideal raw material, soften but honeycomb ceramic carrier exists suction, element wall is thicker, exhaust resistance is larger, the shortcomings such as bad mechanical strength.The metallic carrier wall thickness only is 1/4 of ceramic monolith, thereby can reduce exhaust resistance, and makes the catalyst carrier miniaturization become possibility; The thermal capacity of metallic carrier is little, and pre-good in thermal property is conducive to electric pre-heating catalyst when low temperature.The mechanical strength of metallic carrier and resistance to water are also fine.Be tridimensional network such as Ni-Cr-A1 alloy porous body.The aperture is 0.1mm, and voidage is 85%, and the aperture of ceramic porous article is 0.02mm, and voidage is 50%.The processability of metallic carrier is also much better than pottery.But it is little that the weakness of metallic carrier is specific area, and the load capacity of catalyst is little.
The difficult point of auto-exhaust catalyst is: require the catalyst can be simultaneously with CO, C
mH
nBe oxidized to CO
2With water and with NO original position N also
2And O
2, this is a very harsh requirement, except precious metal, the catalyst of other element is difficult to reach effect like this, even precious metal, to NO
xCapacity of decomposition also be extremely limited, present international cleaning catalyst for tail gases of automobiles mostly is single precious metal catalyst and single carrier model, single precious metal catalyst except costliness, can not 100% be removed CO, NO simultaneously
xAnd C
mH
n, particularly for NO
xEven, in temperature up to 800
℃In time, also be difficult to decompose fully, and NO
xBe pollutant the most serious in the tail gas, mobilize the stage NO cold
xDecompose effect poorer.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, the preparation method of two sections triple effect purifying vehicle exhaust non-precious metal catalysts is provided, the technical solution adopted for the present invention to solve the technical problems is, two sections carriers are ceramic monolith and metallic carrier, metallic carrier be stainless steel and or nickel-chromium-aluminium alloy, will pass through surface preparation, its specific area is at 100m after the preliminary treatment
2/ g, one section catalyst is the rare earth-transition metal oxide, its structural group becomes Ln
1-xM
xBO
3(Ln is rare earth element, and M is alkali earth metal, and B is transition metal, x=0-1) or Ln
2-xM
xBO
4(Ln is rare earth element, M is alkali earth metal, B is transition metal, x=0-1), this catalyst is nanocatalyst, the oxidation of specially taking charge of hydrocarbon, carbon monoxide and carbon granule, be carbon dioxide at 100 ℃ of energy with the carbon monoxide complete oxidation, being carbon dioxide and water with oxidizing hydrocarbon more than 500 ℃, can more than 400 ℃ carbon granule be oxidized to carbon dioxide, the second segment catalyst is Ln
2-xB
xCuO
4(Ln is rare earth element, B=Ce, Sr; X=0-1) nanofiber, specific area is at 105m
2/ g, this Ln
2-xB
xCuO
4(Ln is rare earth element, B=Ce, Sr; X=0-1) nano-fiber catalyst can be nitrogen and oxygen at 300 ℃ of thorough decomposing N O, and two-stage catalytic agent acting in conjunction can thoroughly be converted into innocuous substance carbon dioxide, water and nitrogen and oxygen with the hydrocarbon in the tail gas, carbon monoxide carbon granule and nitrogen oxide at last.
The preparation method is:
One, the surface preparation of metallic carrier: (1), stainless steel wire mesh and or nickel-chromium-aluminium alloy net in distilled water, in 80～100 ℃, under ultrasonic state, cleaned 30～60 minutes; (2), ultrasonic cleaning 30～100 minutes under room temperature in ethanol; (3), with the stainless steel wire mesh after process (1) and (2) and or nickel-chromium-aluminium alloy net place quartz ampoule, again quartz ampoule is placed Muffle furnace, distilled water is contained in the triangular glass bottle, be heated to 80～100 ℃, with the water vapour in the triangular glass bottle by nitrogen bring in the quartz ampoule in the Muffle furnace with stainless steel wire mesh with or nickel-chromium-aluminium alloy net contact, the flow velocity of nitrogen is between 10～50ml/min.Muffle furnace is heated to 200～500 ℃, and the steam treatment time is between 1～5 hour, the stainless steel metal of acquisition and or the specific area of nickel-chromium-aluminium alloy metal at 100m
2/ g;
Two, Ln
1-xM
xBO
3(Ln is rare earth element, and M is alkali earth metal, and B is transition metal, x=0-1) or Ln
2-xM
xBO
4(Ln is rare earth element, M is alkali earth metal, B is transition metal, x=0-1) preparation and load: with rare earth element (such as lanthanum, cerium), alkaline-earth metal is (such as strontium, calcium), transition metal is (such as manganese, iron, cobalt, nickel) nitrate raw material is made into the aqueous solution (concentration of aqueous solution 0.1～0.5N) by the stoichiometry mixing, add citric acid (accounting between the aqueous solution weight ratio 1%～5%), then carrier (ceramic monolith and or metallic carrier) is soaked in the solution, 60～80 ℃ of heating slow evaporations are to doing, 60～120 ℃ of oven dry, again 600～800 ℃ of roastings 3～10 hours, be cooled to room temperature, take out carrier, the above has supported catalyst;
Three, CNT is synthetic, CNT by methane under 600～800 ℃ at LaNiO
3Cracking gets on the catalyst: LaNiO
3The preparation of catalyst, with the nitrate of lanthanum, nickel (La, Ni) by chemical ratios miscible in deionized water (concentration of aqueous solution 0.1～0.5N), add citric acid (accounting between the aqueous solution weight ratio 1%～5%), in 60～80 ℃ of heating slow evaporations to doing, 60～120 ℃ of oven dry, made in 3～10 hours 600～800 ℃ of roastings again; The preparation of CNT is with LaNiO
3Catalyst is put into quartz ampoule, quartz ampoule is placed Muffle furnace, lead to first nitrogen (flow velocity: 10～60ml/min), then switch to hydrogen (flow velocity: 10～30ml/min), rising temperature to 300～800 ℃, reduced 1～5 hour, hydrogen is switched to methane (flow velocity: 10～30ml/min), maintain the temperature at 600～800 ℃, cracking methane 3～10 hours, the product of methane cracking comprises CNT and hydrogen, and methane is switched back nitrogen again, be cooled to room temperature, be the mixture of CNT and catalyst this moment in the quartz ampoule.With LaNiO
3Catalyst and CNT take out from quartz ampoule, repeatedly clean 3～5 times with distilled water and rare nitric acid, obtain the CNT of purifying, and CNT is multi-walled carbon nano-tubes, and tube wall is 5～50 layers of graphite linings, and internal diameter is in 5～30 nanometers;
Four, Ln
2-xB
xCuO
4(Ln is rare earth element, B=Ce, Sr; X=0-1) preparation of nanofiber and the load on carrier: first with lanthanum, copper and or the nitrate raw material of cerium be made into the aqueous solution (concentration of aqueous solution 0.1～0.5N) by stoichiometry, add as stated above homemade multi-walled carbon nano-tubes, total addition of CNT, account for 1～5wt% of aqueous solution gross weight, add high molecular surfactant such as PEO and or polyacrylic acid, account for 1～10wt% of aqueous solution gross weight, disperse through ultrasonic wave, catalyst carrier (ceramic monolith and or metallic carrier) is put into the autoclave that is lined with polytetrafluoroethylene (PTFE) together, dispose 10～40 hours in 60～80 ℃ of constant temperature, be cooled to room temperature, the taking-up carrier of uncapping, carrier is used distilled water flushing repeatedly, then place baking oven in 80～120 ℃ of oven dry, then in Muffle furnace in 500～700 ℃ of roastings 3～5 hours, be taken out to cooling;
Five, will support Ln
1-xM
xBO
3(Ln is rare earth element, and M is alkali earth metal, and B is transition metal, x=0-1) or Ln
2-xM
xBO
4(Ln is rare earth element, and M is alkali earth metal, and B is transition metal, ceramic monolith x=0-1) or metallic carrier and supported Ln
2-xB
xCuO
4(Ln is rare earth element, B=Ce, Sr; X=0-1) ceramic monolith of nano-fiber catalyst or metallic carrier connect, and adopt the silica wool parcel shockproof, and it is jack horse test bed that assembling is placed on vehicle exhaust, moves 1～3 month, gets final product the concentration of detection of hydrocarbon, carbon monoxide and nitrogen oxide.
The invention has the beneficial effects as follows, the hydrocarbon in the tail gas, carbon monoxide carbon granule and nitrogen oxide thoroughly can be converted into innocuous substance carbon dioxide, water and nitrogen and oxygen.
The specific embodiment
One, the surface preparation of metallic carrier: (1), stainless steel wire mesh and or nickel-chromium-aluminium alloy net in distilled water, in 80～100 ℃, under ultrasonic state, cleaned 30～60 minutes; (2), ultrasonic cleaning 30～100 minutes under room temperature in ethanol; (3), with the stainless steel wire mesh after process (1) and (2) and or nickel-chromium-aluminium alloy net place quartz ampoule, again quartz ampoule is placed Muffle furnace, distilled water is contained in the triangular glass bottle, be heated to 80～100 ℃, with the water vapour in the triangular glass bottle by nitrogen bring in the quartz ampoule in the Muffle furnace with stainless steel wire mesh with or nickel-chromium-aluminium alloy net contact, the flow velocity of nitrogen is between 10～50ml/min.Muffle furnace is heated to 200～500 ℃, and the steam treatment time is between 1～5 hour, the stainless steel metal of acquisition and or the specific area of nickel-chromium-aluminium alloy metal at 100m
2/ g;
Two, Ln
1-xM
xBO
3(Ln is rare earth element, and M is alkali earth metal, and B is transition metal, x=0-1) or Ln
2-xM
xBO
4(Ln is rare earth element, M is alkali earth metal, B is transition metal, x=0-1) preparation and load: with rare earth element (such as lanthanum, cerium), alkaline-earth metal is (such as strontium, calcium), transition metal is (such as manganese, iron, cobalt, nickel) nitrate raw material is made into the aqueous solution (concentration of aqueous solution 0.1～0.5N) by the stoichiometry mixing, add citric acid (accounting between the aqueous solution weight ratio 1%～5%), then carrier (ceramic monolith and or metallic carrier) is soaked in the solution, 60～80 ℃ of heating slow evaporations are to doing, 60～120 ℃ of oven dry, again 600～800 ℃ of roastings 3～10 hours, be cooled to room temperature, take out carrier, the above has supported catalyst;
Three, CNT is synthetic, CNT by methane under 600～800 ℃ at LaNiO
3Cracking gets on the catalyst: LaNiO
3The preparation of catalyst, with the nitrate of lanthanum, nickel (La, Ni) by chemical ratios miscible in deionized water (concentration of aqueous solution 0.1～0.5N), add citric acid (accounting between the aqueous solution weight ratio 1%～5%), in 60～80 ℃ of heating slow evaporations to doing, 60～120 ℃ of oven dry, made in 3～10 hours 600～800 ℃ of roastings again; The preparation of CNT is with LaNiO
3Catalyst is put into quartz ampoule, quartz ampoule is placed Muffle furnace, lead to first nitrogen (flow velocity: 10～60ml/min), then switch to hydrogen (flow velocity: 10～30ml/min), rising temperature to 300～800 ℃, reduced 1～5 hour, hydrogen is switched to methane (flow velocity: 10～30ml/min), maintain the temperature at 600～800 ℃, cracking methane 3～10 hours, the product of methane cracking comprises CNT and hydrogen, and methane is switched back nitrogen again, be cooled to room temperature, be the mixture of CNT and catalyst this moment in the quartz ampoule.With LaNiO
3Catalyst and CNT take out from quartz ampoule, repeatedly clean 3～5 times with distilled water and rare nitric acid, obtain the CNT of purifying, and CNT is multi-walled carbon nano-tubes, and tube wall is 5～50 layers of graphite linings, and internal diameter is in 5～30 nanometers;
Four, Ln
2-xB
xCuO
4(Ln is rare earth element, B=Ce, Sr; X=0-1) preparation of nanofiber and the load on carrier: first with lanthanum, copper and or the nitrate raw material of cerium be made into the aqueous solution (concentration of aqueous solution 0.1～0.5N) by stoichiometry, add as stated above homemade multi-walled carbon nano-tubes, total addition of CNT, account for 1～5wt% of aqueous solution gross weight, add high molecular surfactant such as PEO and or polyacrylic acid, account for 1～10wt% of aqueous solution gross weight, disperse through ultrasonic wave, catalyst carrier (ceramic monolith and or metallic carrier) is put into the autoclave that is lined with polytetrafluoroethylene (PTFE) together, dispose 10～40 hours in 60～80 ℃ of constant temperature, be cooled to room temperature, the taking-up carrier of uncapping, carrier is used distilled water flushing repeatedly, then place baking oven in 80～120 ℃ of oven dry, then in Muffle furnace in 500～700 ℃ of roastings 3～5 hours, be taken out to cooling;
Five, will support Ln
1-xM
xBO
3(Ln is rare earth element, and M is alkali earth metal, and B is transition metal, x=0-1) or Ln
2-xM
xBO
4(Ln is rare earth element, and M is alkali earth metal, and B is transition metal, ceramic monolith x=0-1) or metallic carrier and supported Ln
2-xB
xCuO
4(Ln is rare earth element, B=Ce, Sr; X=0-1) ceramic monolith of nano-fiber catalyst or metallic carrier connect, and adopt the silica wool parcel shockproof, and it is jack horse test bed that assembling is placed on vehicle exhaust, moves 1～3 month, gets final product the concentration of detection of hydrocarbon, carbon monoxide and nitrogen oxide.
Embodiment recited above is described preferred embodiment of the present invention; be not that the spirit and scope of the present invention are limited; under the prerequisite that does not break away from design concept of the present invention; common engineers and technicians make technical scheme of the present invention in this area various modification and improvement; all should fall into protection scope of the present invention; the technology contents that the present invention asks for protection all is documented in claims.
Claims (1)
1. two sections triple effect purifying vehicle exhaust non-precious metal catalysts, two sections carriers are ceramic monolith and metallic carrier, metallic carrier be stainless steel and or nickel-chromium-aluminium alloy, pass through surface preparation, its specific area is at 100m after the preliminary treatment
2/ g, one section catalyst is the rare earth-transition metal oxide, its structural group becomes Ln
1-xM
xBO
3(Ln is rare earth element, and M is alkali earth metal, and B is transition metal, x=0-1) or Ln
2-xM
xBO
4(Ln is rare earth element, M is alkali earth metal, B is transition metal, x=0-1), this catalyst is nanocatalyst, the oxidation of specially taking charge of hydrocarbon, carbon monoxide and carbon granule, be carbon dioxide at 100 ℃ of energy with the carbon monoxide complete oxidation, being carbon dioxide and water with oxidizing hydrocarbon more than 500 ℃, can more than 400 ℃ carbon granule be oxidized to carbon dioxide, the second segment catalyst is Ln
2-xB
xCuO
4(Ln is rare earth element, B=Ce, Sr; X=0-1) nanofiber, specific area is at 105m
2/ g, this Ln
2-xB
xCuO
4(Ln is rare earth element, B=Ce, Sr; X=0-1) nano-fiber catalyst can be nitrogen and oxygen at 300 ℃ of thorough decomposing N O, two-stage catalytic agent acting in conjunction can thoroughly be converted into innocuous substance carbon dioxide, water and nitrogen and oxygen with the hydrocarbon in the tail gas, carbon monoxide carbon granule and nitrogen oxide at last, it is characterized in that the preparation method of two sections triple effect purifying vehicle exhaust non-precious metal catalysts is:
One, the surface preparation of metallic carrier: (1), stainless steel wire mesh and or nickel-chromium-aluminium alloy net in distilled water, in 80～100 ℃, under ultrasonic state, cleaned 30～60 minutes; (2), ultrasonic cleaning 30～100 minutes under room temperature in ethanol; (3), with the stainless steel wire mesh after process (1) and (2) and or nickel-chromium-aluminium alloy net place quartz ampoule, again quartz ampoule is placed Muffle furnace, distilled water is contained in the triangular glass bottle, be heated to 80～100 ℃, with the water vapour in the triangular glass bottle by nitrogen bring in the quartz ampoule in the Muffle furnace with stainless steel wire mesh with or nickel-chromium-aluminium alloy net contact, the flow velocity of nitrogen is between 10～50ml/min.Muffle furnace is heated to 200～500 ℃, and the steam treatment time is between 1～5 hour, the stainless steel metal of acquisition and or the specific area of nickel-chromium-aluminium alloy metal at 100m
2/ g;
Two, Ln
1-xM
xBO
3(Ln is rare earth element, and M is alkali earth metal, and B is transition metal, x=0-1) or Ln
2-xM
xBO
4(Ln is rare earth element, M is alkali earth metal, B is transition metal, x=0-1) preparation and load: with rare earth element (such as lanthanum, cerium), alkaline-earth metal is (such as strontium, calcium), transition metal is (such as manganese, iron, cobalt, nickel) nitrate raw material is made into the aqueous solution (concentration of aqueous solution 0.1～0.5N) by the stoichiometry mixing, add citric acid (accounting between the aqueous solution weight ratio 1%～5%), then carrier (ceramic monolith and or metallic carrier) is soaked in the solution, 60～80 ℃ of heating slow evaporations are to doing, 60～120 ℃ of oven dry, again 600～800 ℃ of roastings 3～10 hours, be cooled to room temperature, take out carrier, the above has supported catalyst;
Three, CNT is synthetic, CNT by methane under 600～800 ℃ at LaNiO
3Cracking gets on the catalyst: LaNiO
3The preparation of catalyst, with the nitrate of lanthanum, nickel (La, Ni) by chemical ratios miscible in deionized water (concentration of aqueous solution 0.1～0.5N), add citric acid (accounting between the aqueous solution weight ratio 1%～5%), in 60～80 ℃ of heating slow evaporations to doing, 60～120 ℃ of oven dry, made in 3～10 hours 600～800 ℃ of roastings again; The preparation of CNT is with LaNiO
3Catalyst is put into quartz ampoule, quartz ampoule is placed Muffle furnace, lead to first nitrogen (flow velocity: 10～60ml/min), then switch to hydrogen (flow velocity: 10～30ml/min), rising temperature to 300～800 ℃, reduced 1～5 hour, hydrogen is switched to methane (flow velocity: 10～30ml/min), maintain the temperature at 600～800 ℃, cracking methane 3～10 hours, the product of methane cracking comprises CNT and hydrogen, and methane is switched back nitrogen again, be cooled to room temperature, be the mixture of CNT and catalyst this moment in the quartz ampoule.With LaNiO
3Catalyst and CNT take out from quartz ampoule, repeatedly clean 3～5 times with distilled water and rare nitric acid, obtain the CNT of purifying, and CNT is multi-walled carbon nano-tubes, and tube wall is 5～50 layers of graphite linings, and internal diameter is in 5～30 nanometers;
Four, Ln
2-xB
xCuO
4(Ln is rare earth element, B=Ce, Sr; X=0-1) preparation of nanofiber and the load on carrier: first with lanthanum, copper and or the nitrate raw material of cerium be made into the aqueous solution (concentration of aqueous solution 0.1～0.5N) by stoichiometry, add as stated above homemade multi-walled carbon nano-tubes, total addition of CNT, account for 1～5wt% of aqueous solution gross weight, add high molecular surfactant such as PEO and or polyacrylic acid, account for 1～10wt% of aqueous solution gross weight, disperse through ultrasonic wave, catalyst carrier (ceramic monolith and or metallic carrier) is put into the autoclave that is lined with polytetrafluoroethylene (PTFE) together, dispose 10～40 hours in 60～80 ℃ of constant temperature, be cooled to room temperature, the taking-up carrier of uncapping, carrier is used distilled water flushing repeatedly, then place baking oven in 80～120 ℃ of oven dry, then in Muffle furnace in 500～700 ℃ of roastings 3～5 hours, be taken out to cooling.
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| CN103599789A (en) * | 2013-11-01 | 2014-02-26 | 中国科学院福建物质结构研究所 | Perovskite-type catalyst for selective catalytic reduction of nitrogen oxides |
| CN103785374A (en) * | 2014-02-20 | 2014-05-14 | 重庆大学 | C (carbon) nano tube demercuration catalyst and preparation method thereof |
| CN105363451A (en) * | 2015-12-04 | 2016-03-02 | 中国天辰工程有限公司 | Efficient catalyst for decomposition of N2O and preparation method and application thereof |
| US9662636B2 (en) | 2014-04-17 | 2017-05-30 | Basf Corporation | Zoned catalyst composites |
| CN113215621A (en) * | 2021-04-13 | 2021-08-06 | 昆明理工大学 | Method for recovering noble metal from catalyst containing noble metal |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000167402A (en) * | 1998-12-09 | 2000-06-20 | Daihatsu Motor Co Ltd | Catalyst for purification of exhaust gas |
| CN101036888A (en) * | 2007-04-26 | 2007-09-19 | 天津大学 | Perovskite fiber boy compound oxide catalyst for treating automobile's waste gas, and method for preparing same |
| CN101468295A (en) * | 2007-12-28 | 2009-07-01 | 中国石油大学(北京) | Combined catalyst for simultaneously eliminating four kinds of pollutants from diesel exhaust and purification method |
| JP2009154086A (en) * | 2007-12-26 | 2009-07-16 | Honda Motor Co Ltd | Catalyst for clarifying exhaust gas |
| CN101845306A (en) * | 2010-03-31 | 2010-09-29 | 天津大学 | Preparation method and application of Lal-xSrxCoO3 perovskite catalyst |
| CN102125855A (en) * | 2010-12-29 | 2011-07-20 | 天津大学 | SiOC porous ceramic supported La0.9K0.1CoO3 nano particle catalyst and preparation method |
| CN102247836A (en) * | 2011-05-25 | 2011-11-23 | 天津大学 | Rare-earth perovskite type catalyst for purifying automobile tail gas and preparation method |
| CN102247859A (en) * | 2011-05-25 | 2011-11-23 | 天津大学 | Perovskite-like catalyst used for purifying automobile tail gas, and preparation method thereof |
| CN102626632A (en) * | 2012-03-19 | 2012-08-08 | 天津大学 | Perovskite catalyst capable of removing nitrogen oxides and soot in diesel exhaust simultaneously and its preparation method and use |
-
2012
- 2012-10-09 CN CN201210391530.4A patent/CN102909024B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000167402A (en) * | 1998-12-09 | 2000-06-20 | Daihatsu Motor Co Ltd | Catalyst for purification of exhaust gas |
| CN101036888A (en) * | 2007-04-26 | 2007-09-19 | 天津大学 | Perovskite fiber boy compound oxide catalyst for treating automobile's waste gas, and method for preparing same |
| JP2009154086A (en) * | 2007-12-26 | 2009-07-16 | Honda Motor Co Ltd | Catalyst for clarifying exhaust gas |
| CN101468295A (en) * | 2007-12-28 | 2009-07-01 | 中国石油大学(北京) | Combined catalyst for simultaneously eliminating four kinds of pollutants from diesel exhaust and purification method |
| CN101845306A (en) * | 2010-03-31 | 2010-09-29 | 天津大学 | Preparation method and application of Lal-xSrxCoO3 perovskite catalyst |
| CN102125855A (en) * | 2010-12-29 | 2011-07-20 | 天津大学 | SiOC porous ceramic supported La0.9K0.1CoO3 nano particle catalyst and preparation method |
| CN102247836A (en) * | 2011-05-25 | 2011-11-23 | 天津大学 | Rare-earth perovskite type catalyst for purifying automobile tail gas and preparation method |
| CN102247859A (en) * | 2011-05-25 | 2011-11-23 | 天津大学 | Perovskite-like catalyst used for purifying automobile tail gas, and preparation method thereof |
| CN102626632A (en) * | 2012-03-19 | 2012-08-08 | 天津大学 | Perovskite catalyst capable of removing nitrogen oxides and soot in diesel exhaust simultaneously and its preparation method and use |
Non-Patent Citations (2)
| Title |
|---|
| 汪仁等: "非贵金属汽车排气净化催化剂的研究—蜂窝状非贵金属催化剂的研究", 《华东化工学院学报》 * |
| 王亚军等: "汽车尾气净化催化剂载体", 《工业催化》 * |
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|---|---|---|---|---|
| CN103352777A (en) * | 2013-05-31 | 2013-10-16 | 广西地凯科技有限公司 | Hydrogen engine system |
| CN103352777B (en) * | 2013-05-31 | 2017-02-22 | 广西地凯科技有限公司 | Hydrogen engine system |
| CN103599789A (en) * | 2013-11-01 | 2014-02-26 | 中国科学院福建物质结构研究所 | Perovskite-type catalyst for selective catalytic reduction of nitrogen oxides |
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| US9662636B2 (en) | 2014-04-17 | 2017-05-30 | Basf Corporation | Zoned catalyst composites |
| CN105363451A (en) * | 2015-12-04 | 2016-03-02 | 中国天辰工程有限公司 | Efficient catalyst for decomposition of N2O and preparation method and application thereof |
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